Oil-soluble ceric salts and method of preparing the same



Unite States OIL-SOLUBLE CERIC SALTS AND METHOD F PREPARING THE SAMESamuel Kaizerman, North Plainfield, and Guido Mino,

Plainfield, N.J., assignors to American Cyanamid Company, New York,N.Y., a corporation of Maine No Drawing. Application June 3, 1958 SerialNo. 739,458

20 Claims. (Cl. 260-4292) utility particularly as graft polymerizationinitiators in a vinyl polymerization system. These and other objects ofthe'present invention will be discussed in greater detail hereinbelow.

This application is a continuation-in-part of our earlier applicationhaving the Serial No. 628,212, filed December 14, 1956, entitled Processfor Polymerization and the Products Produced Thereby. Said applicationis a continuation-in-part of our parent case having the Serial No.

577,641, filed April 12, 1956, entitled Process for Polymerization andthe Products Produced Thereby, now abandoned.

In producing the novel oil-soluble ceric salts of the present invention,one may react an inorganic ceric salt with an alkali metal salt of amaterial selected from the group consisting of an alkyl sulfate, analkyl mono aromaticsulfonate, a sulfonate of an aliphatic polycarboxylicacid dialkyl ester and an aliphatic hydrocarbon sulfonate. The inorganicceric salts may be any one of the following: ceric nitrate, cericammonium nitrate, ceric perchlorate and the like. These inorganic cericsalts may be used'either singly or in combination with one another.

The alkali metal salts used as starting materials in the practice of theprocess of the present invention may be the sodium salts, potassiumsalts, lithium salts, and the like. Included in the group of alkalimetal salts which may be used are sodium monobutyl acid sulfate,potassium monoamyl acid sulfate, sodium monooctyl acid sulfate, sodiummonolauryl acid sulfate, potassium monodecyl acid sulfate, lithiummono-undecyl acid sulfate, sodium octyl benzene sulfonate, potassiumdecyl benzene sulfonate, sodium dioctyl sulfosuccinate, lithium diheptylsulfoglutarate, potassium didecyl sulfosuberate, sodium dilaurylsulfosebacate, potassium diamyl sulfomaleate, sodium dimethylsulfofumarate, sodium dibutyl sulfodimethyl succinate, potassiumdilauryl sulfomethyl glutarate, sodium butyl sulfonate, potassium hexylsul-- fonate, lithium octyl sulfonate, potassium decyl sulfonate, sodiumdodecyl sulfonate, and the like. 7

Among the oil-soluble ceric alkyl sulfates which may be preparedaccording to the process of the present invention are those ceric alkylsulfates in which the alkyl group contains between 4 and 20 carbon atomsand preferably between 8 and 12 carbon atoms. Included in .the group areceric butyl sulfate, ceric amyl sulfate, ceric hexyl sulfate, cericheptyl sulfate, ceric octyl sulfate, ceric nonyl sulfate, ceric decylsulfate, ceric undecyl sulfate,

atent methyl sulfofumarate,

ice

ceric dodecyl sulfate, ceric tridecyl sulfate, ceric tetradecyl sulfate,ceric pentadecyl sulfate, ceric hexadecyl sulfate, ceric heptadecylsulfate, ceric octadecyl sulfate, ceric nonadecyl sulfate, and cericeicosyl sulfate. The alkyl groups in these ceric alkyl sulfates may beeither a straight chain or a branch chain.

Among the oil-soluble ceric alkyl mono aromatic sulfonates which may beprepared according to the present invention are those in which the alkylgroups attached to the mono aromatic ring contain between 3 and 20carbon atoms, and preferably between 8 and 12 carbon atoms. The monoaromatic grouping in said sulfonates may be phenyl, naphthyl, anthracyl,triphenylyl, perylyl, and the like. More specifically, these compoundsinclude ceric butyl benzene sulfonate, ceric hexyl benzene sulfonate,ceric octyl benzene sulfonate, ceric nonyl benzene sulfonate, cericdecyl benzene sulfonate, ceric dodecyl benzene sulfonate, cericoctadecyl benzene sulfonate, ceric isopropyl naphthalene sulfonate,ceric heptyl naphthalene sulfonate, ceric tetradecyl naphthalenesulfonate, ceric heptadecyl naphthalene sulfonate, ceric eicosylnaphthalene sulfonate, and the like.

Among the oil-soluble ceric sulfonates of an aliphatic polycarboxylicacid dialkyl ester which may be prepared from the process of the presentinvention are those prepared from the sodium salts of a sulfonate of analiphatic polycarboxylic acid dialkyl ester. These sodium salts andother alkali metal salts are shown in considerable detail in the US.Patent 2,028,091. The aliphatic dicarboxylic acids which may be used asstarting materials include malonic, succinic, glutaric, sebacic, adipic,pimelic, suberic, azelaic, citric, tartaric, malic, maleic, fumaric,aconitic, itaconic, and the like. The diesters of these acids areprepared by reacting an aliphatic monohydric alcohol containing from 1to 15 carbon atoms and preferably containing from 4 to 8 carbon atoms soas to form the dialkyl ester of said polycarboxylic acid. Morespecifically the following oil-soluble ceric salts may be prepared bythe process of the present invention: ceric dihexyl sulfosuccinate,ceric dioctyl sulfosuccinate, ceric diheptyl sulfoglutarate, cericdidecyl sulfosubarate, ceric dilauryl sulfosebacate, ceric diamylsulfomaleate, ceric diceric dibutyl sulfodimethyl succinate, cericdilauryl sulfomethyl glutarate, ceric dipentadecyl sulfosuccinate, andthe like.

Among the oil-soluble ceric aliphatic hydrocarbon sulfonates which maybe prepared in keeping with the process of the present invention arethose in which the aliphatic hydrocarbon contains between 4 and 20carbon atoms and preferably those containing between 8 and 12 carbonatoms. More specifically, the oil-soluble ceric aliphatic hydrocarbonsulfonates of the present invention include ceric butyl sulfonate, cericamyl sulfonate, ceric hexyl sulfonate, ceric octyl sulfonate, cericdecyl sulfonate, ceric dodecyl sulfonate, ceric tetradecyl sulfonate,ceric hexadecyl sulfonate, ceric octadecyl sulfonate, ceric eicosylsulfonate, and the like.

In the practice of the process of the present invention, the inorganicceric salt is introduced into the reaction sphere with an alkali metalsalt of an alkyl sulfate or an alkyl mono aromatic sulfonate or asulfonate of an aliphatic polycarboxylic acid dialkyl ester or analiphatic hydrocarbon sulfonate in an aqueous medium. The temperature ofthe reaction may be controlled between about 0 C. and 40 C. andpreferably between 20 and 25 C .The pH of the system should be adjustedto 3.5 or below and preferably between about 1 and 2. The system will berendered acidic by the use of an acid material and preferably aninorganic acid material such as nitric acid,

perchloric acid, and the like. In order to insure substanmono aromaticsulfonates or the sulfonates of an aliphatic polycarboxylic acid dialkylester or the aliphatic hydrocarbon sulfonates, agitation is preferred ascontrasted with quiescence in the course of reaction. For satisfactoryyields, one should use at least 1 mol Ofthe alkali metal sulfate orsulfonate per mol of the eerie inorganic salt and as much as 4 mols ofthe alkali metal sulfate or sulfonate per mol of the ceric inorganicsalt. Larger quantities of the alkali metal sulfate or sulfonate may beused such as 5 mols or even 6 but no appreciable advantage is to begained. It is preferred that the mol ratio of the alkali metal sulfatesor sulfonates per mol of ceric inorganic salt be controlled betweenabout 1.521 and 2:1, respectively.

The novel oil-soluble ceric salts'of the present invention will findutility in the polymerization of polymerizable monomeric compounds suchas styrene, acrylonitrile, vinyl acetate, acrylamide, and the like, andparticularly in a system in which a grafting mechanism is being carriedout with a polymeric organic reducing agent such as when an aqueousemulsion system is utilized.

In order that the concept of the present invention may be morecompletely understood, the following examples are set forth in which allparts are parts by weight unless otherwise indicated. These examples areset forth primarily for the purpose of illustration and any specificenumeration of detail contained therein should not be interpreted as alimitation on the case except as is indicated in the appended claims. a7

Example 1 Into a suitable reaction vessel equipped with a mechanicalstirrer, there is introduced a solution of 11 parts of ceric ammoniumnitrate in 100 parts of water at room temperature. With constantstirring, there is added thereto a solution of 15.4-parts of sodiumdihexyl sulfosuccinate in 100 parts of water. The stirring is continuedeven after the addition is completed and is stopped only when all of theprecipitate has come out of the blended solutions. The precipitate isseparated from the water by a simple filtration producing a yield of 14parts of ceric dihexyl sulfosuccinate. 7

Example 2 parts of a 0.1 molar solution of nitric acid at 15 C.

The resulting yellow precipitate, after separation by filtra: tion anddrying in vacuo at C., weighed 12.6 parts and was identified as cericdiamyl sulfosuccinate.

Example 3 11 parts of ceric ammonium nitrate are dissolved in 100 partsof a 0.1 molar solution of nitric acid at 25 C. To this solution thereis added, with rapid stirring,

a solution of 13.8 parts of sodium dodecyl benzene sulfonate in 100parts of water. The yellow precipitate which formed was separated byfiltration and dried in vacuo at 45 C. The yield was 4.8 parts and wasidentified as ceric dodecyl benzene sulfonate. The ceric salt thusproduced was soluble in' ethyl acetate, benzene and chloroform. v 7

Example 4 y seesh eri e and mete 1. m re.

fate and was soluble in benzene, methyl acrylate, meth- 11 parts ofceric ammonium nitrate are dissolved in parts of 0.1 N nitric acid at 20C. To this is added with rapid stirring a solution of 8.7 parts ofsodium octane sulfonate in 100 parts ofwater. The yellow precipitate isseparated by filtration, washed with water, then dried in vacuo at 4045C. The yield is 5.7 parts.

The term oil soluble is one frequently used in the art and signifiessolubility in an organic solvent, which sol: vent is itself not misciblewith water. A plurality of these solvents have been recited hereinaboveand a substantial plurality of said solvents are well known in the art.

Further delineation is deemed to be unnecessary.

We claim:

1. An oil-soluble ceric salt selected from the group consisting of (1) aceric alkyl sulfate, (2) a ceric alkyl arene sulfonate, (3) a cericsulfonate of an unsubstituted aliphatic polycarboxylic acid dialkylester and (4) a ceric aliphatic hydrocarbon sulfonate.

2, An oil-soluble ceric alkyl sulfate.

3.'An oil-soluble ceric alkyl arene sulfonate.

4,. An oil-soluble ceric sulfonate of an unsubstituted aliphaticpolycarboxylic acid dialkyl ester. 5. An oil-soluble ceric aliphatichydrocarbon sulfonate.

6. Ceric dihexyl sulfosuccinate. '7. Ceric diamyl sulfosuccinate.

8. Ceric dodecyl benzene sultonate.

9. Ceric dodecyl sulfate.

10. ,Ceric dodecyl sulfonate.

11, A method for preparing an .oil-soluble ceric salt which comprisesreacting an inorganic ceric salt selected from the group consisting ofceric nitrate, ceric ammonium nitrate and ceric perchlorate with analkali metal salt of a material selected from the group consisting of(1) an alkyl sulfate, (2) an alkyl arene sulfonate, (3) a sulfonate ofan unsubstituted aliphatic polycarboxylic acid dialkyl ester and (4) analiphatic hydrocarbon sulfonate. g

12. A method for preparing an oil-soluble ceric comprising reacting aninorganic ceric salt selected from the group consisting of cericnitrate, ceric ammonium comprising reactlng an inorganic ceric saltselected from the group consisting of'ceric nitrate, ceric ammoniumnitrate and ceric perchlorate with an alkali metal salt of an alkylarene sulfonate.

14. A method for preparing an oil-soluble ceric salt comprising reactingan inorganic ceric salt selected from the group consisting of cericnitrate, ceric ammonium nitrate and ceric perchlorate with an alkalimetal salt of a sulfonate of an unsubstituted aliphaticpolycarboxylicacid dialkyl ester.

15. A method for preparing an oil-soluble ceric salt comprising reactingan inorganic ceric salt selected from the group consisting of cericnitrate, ceric ammonium nitrate and ceric perchlorate with an alkalimetal salt of an aliphati hydrocarbon .sulfonate. V

16. A method comprising reacting ceric ammonium nitrate with sodiumdihexyl sulfosuccinate. V f

17. A process comprising reacting, ceric ammonium nitrate with sodiumdiamyl sulfosuccinate. H ,1 "f

18. A process comprising reacting cetjic ammonium nitrate with sodiumdodecyl benzene sulfona'te. i

19. A process comprising reacting ceric ammonium nitrate with sodiumdodecyl sulfate.

.20. A process comprising reacting ceric ammonium nitrate with'sodiumdodecyl'sulfonate.

2,485,535 Park 2 :5 4;50 H wa d.

nitrate and ceric perchlorate with an alkali metal salt of

1. AN OIL-SOLUBLE CERIC SALT SELECTED FROM THE GROUP CONSISTING OF (1) ACERIC ALKYL SULFATE, (2) A CERIC ALKYL ARENE SULFONATE, (3) A CERICSULFONATE OF AN UNSUBSTITUTED ALIPHATIC POLYCARBOXYLIC ACID DIALKYLESTER AND (4) A CERIC ALIPHATIC HYDROCARBON SULFONATE.
 11. A METHOD FORPREPARING AN OIL-SOLUBLE CERIC SALT WHICH COMPRISES REACTING ANINORGANIC CERIC SALT SELECTED FROM THE GROUP CONSISTING OF CERICNITRATE, CERIC AMMONIUM NITRATE AND CERIC PERCHLORATE WITH AN ALKALIMETAL SALT OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF (1) ANALKYL SULFATE, (2) AN ALKYL ARENE SULFONATE, (3) A SULFONATE OFF ANUNSUBSTITUTED ALIPHATIC POLYCARBOXYLIC ACID DIALKYL ESTER AND (4) ANALIPHATIC HYDROCARBON SULFONATE.